US20080057246A1 - Multilayer composite in form of extruded hollow sections - Google Patents
Multilayer composite in form of extruded hollow sections Download PDFInfo
- Publication number
- US20080057246A1 US20080057246A1 US11/831,289 US83128907A US2008057246A1 US 20080057246 A1 US20080057246 A1 US 20080057246A1 US 83128907 A US83128907 A US 83128907A US 2008057246 A1 US2008057246 A1 US 2008057246A1
- Authority
- US
- United States
- Prior art keywords
- polyamide
- layer
- composite according
- layer composite
- hollow section
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 229920002647 polyamide Polymers 0.000 claims abstract description 128
- 239000004952 Polyamide Substances 0.000 claims abstract description 126
- 239000000203 mixture Substances 0.000 claims abstract description 56
- 238000001125 extrusion Methods 0.000 claims abstract description 38
- 229920001971 elastomer Polymers 0.000 claims abstract description 28
- 239000000806 elastomer Substances 0.000 claims abstract description 26
- 229920002614 Polyether block amide Polymers 0.000 claims abstract description 23
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 21
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 20
- -1 ester ether amides Chemical class 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 15
- 229920000570 polyether Polymers 0.000 claims abstract description 15
- 239000000446 fuel Substances 0.000 claims abstract description 13
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 claims abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 48
- 230000004888 barrier function Effects 0.000 claims description 36
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims description 33
- 229920002292 Nylon 6 Polymers 0.000 claims description 32
- 239000004609 Impact Modifier Substances 0.000 claims description 21
- 229920000299 Nylon 12 Polymers 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 19
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 18
- 239000012778 molding material Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- 239000004014 plasticizer Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 9
- 150000004985 diamines Chemical class 0.000 claims description 7
- 229920000571 Nylon 11 Polymers 0.000 claims description 6
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
- 229920002313 fluoropolymer Polymers 0.000 claims description 4
- 239000004811 fluoropolymer Substances 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- 229920006396 polyamide 1012 Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- 230000002787 reinforcement Effects 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 229920006152 PA1010 Polymers 0.000 claims description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004760 aramid Substances 0.000 claims description 3
- 229920003235 aromatic polyamide Polymers 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000012760 heat stabilizer Substances 0.000 claims description 3
- 238000003780 insertion Methods 0.000 claims description 3
- 230000037431 insertion Effects 0.000 claims description 3
- 239000004611 light stabiliser Substances 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 3
- HFVMEOPYDLEHBR-UHFFFAOYSA-N (2-fluorophenyl)-phenylmethanol Chemical compound C=1C=CC=C(F)C=1C(O)C1=CC=CC=C1 HFVMEOPYDLEHBR-UHFFFAOYSA-N 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005700 Putrescine Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 claims description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims description 2
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims 2
- 229920006144 PA618 Polymers 0.000 claims 2
- SPJXZYLLLWOSLQ-UHFFFAOYSA-N 1-[(1-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CCCCC1(N)CC1(N)CCCCC1 SPJXZYLLLWOSLQ-UHFFFAOYSA-N 0.000 claims 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 claims 1
- 229920001610 polycaprolactone Polymers 0.000 claims 1
- 239000004711 α-olefin Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 149
- 238000012360 testing method Methods 0.000 description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 229920003620 Grilon® Polymers 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
- 239000011592 zinc chloride Substances 0.000 description 6
- 229920006659 PA12 Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 235000005074 zinc chloride Nutrition 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013065 commercial product Substances 0.000 description 3
- 239000002482 conductive additive Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000009863 impact test Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000012764 mineral filler Substances 0.000 description 2
- 229920006119 nylon 10T Polymers 0.000 description 2
- 229920006115 poly(dodecamethylene terephthalamide) Polymers 0.000 description 2
- 229920006110 poly(m-benzoyl4,4'-methylenebis(cyclohexylamine)) Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920000393 Nylon 6/6T Polymers 0.000 description 1
- 239000004954 Polyphthalamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000002288 cocrystallisation Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229920006017 homo-polyamide Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920006375 polyphtalamide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- AZSKHRTUXHLAHS-UHFFFAOYSA-N tris(2,4-di-tert-butylphenyl) phosphate Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(=O)(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C AZSKHRTUXHLAHS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a general shape other than plane
- B32B1/08—Tubular products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/12—Polyester-amides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1379—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
- Y10T428/1393—Multilayer [continuous layer]
Definitions
- the present patent application claims priority of European patent application EP 06 015 922.5 and relates to modified polyamide (PA) extrusion molding materials modified with polyamide elastomers (TPE-A) for the improvement of the elongation at break of the extruded article at higher extrusion speed.
- PA modified polyamide
- TPE-A polyamide elastomers
- the invention further relates to multi-layer composites, in particular to thermoplastic multi-layer composites, in form of hollow sections, preferably for the automotive sector, comprising at least one outer layer made from these molding materials as well as at least a further layer, preferably a barrier layer and optionally further layers.
- the present invention relates also to a method for the production of said hollow sections, which may especially exist in the form of tubes, pipes or hoses, preferably for the automotive sector, more preferably as fuel tube or pipe for liquid fuels such as gasoline or diesel or for alternative fuels like e.g. bio ethanol (and appropriate fuel mixtures) or rape methyl esters.
- the above specified effect that at higher extrusion speeds the mechanical characteristics of the manufactured articles are worsening, is already known to experts for a long time and represents a disadvantage, because the extrusion speed is limited thereby.
- the critical point of the multi-layer tube is namely the outer surface, i.e. the surface section of the tube, which cools down most quickly from the outer and which orients itself more distinctly at higher speed. Consequently, due to the higher tension in the outer surface and the smaller elasticity when mechanically loaded, respectively, it begins to break earlier.
- the effect mentioned above is described by e.g. A. Carin et al. in Intern. Polymer Processing XX (2005), pages 305-311. Here one finds on page 310 the well-known relation that the orientation of the outer surface increases with increasing drawdown speed, i.e. the elongation at break decreases vice versa.
- EP 1 452 307 A1 describes multi-layer automotive tubes, which are resistant to peroxide containing gasoline and which also comply to the usual requirements regarding cold impact and which have a simple and economical structure.
- the multi-layer tube is formed with an inner layer based on a mixture of polyamide homopolymers, and it additionally has a compatibilizer.
- the characteristic feature of EP 1 452 307 A1 is the fact that the inner layer is not formed based on only one polyamide homopolymer or based on a mixture of polyamide 6 copolymers, but from a blend of different non-mixable polyamide homopolymers, using a compatibilizer. If this blend is also used for the outer layer of a multi-layer line, as provided in EP 1,452,307 A1, the above mentioned effect also arises, that with increasing extrusion speed the elongation at break of the multi-layer tube is reduced.
- GB 2 390 658 B describes multi-layer polymer tube or hose lines with an ethylene/vinyl alcohol copolymer (abbreviated EVAL or, in the English-speaking world, also designated as EVOH) barrier layer as well as with an outer layer of polyamide 612 or polyamide 610 and an inner layer of polyamide 6, polyamide 612 or polyamide 610.
- EVAL ethylene/vinyl alcohol copolymer
- EVOH ethylene/vinyl alcohol copolymer
- DE 698 31 239 T2 describes multilayered structures based on polyamides, in particular tubes with multilayered structure, wherein at least one inner layer and at least one outer layer are provided.
- the outer layer is formed from a mixture of at least one copolyamide of the type 6/6-36 and at least a second thermoplastic polymer, i.e. of the type polyamide 6.
- the second polymer does not contain plasticizers or elastomers.
- EP-A-1 559 537 describes a multilayered plastic tube with barrier characteristics for automobiles.
- the plastic of the substrate may consist of a blend of polyamides.
- a barrier layer made of EVOH is provided.
- the outer layer of the multilayered fuel tube can additionally have a jacket by an outer protective layer, which consists of a thermoplastic elastomer (TP) and a thermoplastic polyurethane (TPU), respectively.
- TP thermoplastic elastomer
- TPU thermoplastic polyurethane
- thermoplastic multilayered structures which include inner layers made from polyamides or polyamide mixtures.
- the polymer mixtures can contain usual polyamide types without plasticizers.
- EP 0 710 537 A2 describes a multilayered line or conduit, wherein the inner layer consists of polyamides and which outer layer consists of polyamides having a layer of EVOH disposed between.
- the mixtures of the layer materials do not contain plasticizers and/or polyamide elastomers.
- DE 35 10 395 A1 describes multi-layer fuel tubes or hose lines with an alcohol barrier layer based on polyvinyl alcohol.
- an alcohol barrier layer based on polyvinyl alcohol.
- a polyamide protective layer made of polyamide 11 or 12 is provided.
- DE 3 724 997 C2 describes the use of polyamide/polyamide elastomer mixtures in the production of polymer protective layers of fiber-optic cables.
- the coating of fiber-optic cables with a layer of polyamide/polyamide elastomer mixtures is accomplished according to DE 3 724 997 C2 using the extrusion method.
- EP 0 566 755 B 1 further describes polyether amide hoses for medical instruments, which are extruded from a mixture of two polymers, of which one polymer is a polyether amide and the other one is a polyether ester amide or a polyamide.
- thermoplastic multi-layer composite which is improved with regard to the layer adhesion and the resistance regarding resistance to chemicals, permeation as well as resistance to elution, wherein even at higher extrusion speeds only small tensions in the outer surface are to be found, e.g. the mechanical characteristics are not impaired, and the economy of the tubing production can be substantially increased.
- the inventors have now surprisingly found during extrusion experiments of multi-layer tubes, particularly with barrier layers, as e.g. from EVOH (ethylene vinyl alcohol copolymers), that the effect of impairment of the mechanical characteristics in the outer surface can be inverted in a completely unexpected way, if one adds a certain portion of polyamide elastomer to the polyamide molding material provided for the outer layer, in particular if the polyamide elastomer is not mixable with the polyamide.
- barrier layers as e.g. from EVOH (ethylene vinyl alcohol copolymers
- the invention relates to new multi-layer composites, especially to thermoplastic multi-layer composites, in form of an extruded hollow section, comprising a thermoplastic outer layer and at least one further layer, wherein the outer layer is formed of a mixture based on (A) 80 to 20 parts by weight of at least one polyamide (PA) and (B) 20 to 80 parts by weight of at least one polyamide elastomer (TPE-A), the latter from the group of the polyether amides, the polyester amides, the polyether ester amides, the polyether ester ether amides and mixtures thereof, wherein the sum of (A) and (B) results in 100 parts by weight.
- PA polyamide
- TPE-A polyamide elastomer
- the hollow sections with such an outer layer manufactured at higher extrusion speed showing a higher elongation at break, compared to an otherwise identical hollow section, manufactured at lower extrusion speed, as well as particularly also compared with a hollow section with a polyamide outer layer without polyamide elastomer additive, manufactured at the same extrusion speed, wherein the elongation at break is determined on the finished hollow section according to DIN EN ISO 527-2.
- a PA elastomer portion (TPE-A) to the outer layer material, i.e. a polyamide (PA), e.g. 50 parts by weight, related to 100 parts by weight from the sum of PA and TPE-A, already at 20 m/min extrusion speed
- PA polyamide
- elongation at break ⁇ R begins to reach a value of over 200%, in contrast to a multi-layer composite with polyamide outer layer without (TPE-A)-additive and even increases at higher speed (see experiments of table 4 with 40 m/min and 60 m/min), which is particularly amazing.
- the definition of the elongation at break ⁇ R is well-known to a skilled person and can be found e.g. in the book: Kunststoff- Kompendium, 2. Edition, VOGEL Buchverlag Würzburg, 1988, page 239 among the characteristic values.
- polyamide (PA) for the component (A) favorably polycondensation products of aliphatic lactams or ⁇ -aminocarboxylic acids with 4 to 44 carbon atoms, preferably 4 to 18 carbon atoms, or such from aromatic aminocarboxylic acids with 6 to 20 carbon atoms are used.
- polycondensation products from at least one diamine and at least one dicarboxylic acid with 2 to 44 carbon atoms are polycondensation products from at least one diamine and at least one dicarboxylic acid with 2 to 44 carbon atoms, respectively.
- diamines are ethylene diamine, 1,4-diamino butane, 1,6-diamino hexane, 1,10-diamino decane, 1,12-diamino dodecane, m- and p-xylylene diamine, cyclohexyl dimethylene amine, bis-(aminocyclohexyle)methane and its alkyl derivatives.
- dicarboxylic acids examples include succinic, glutaric, adipic, pimelic, suberic, azelaic and sebacic acid, dodecanic diacid, dimer fatty acids with 36 or 44 C-atoms, 1,6-cyclohexane dicarboxylic acid, terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid.
- PA polyamides
- PA polyamides
- PA polyamides
- PA polyamides
- copolymers based on the above mentioned polyamides like e.g. 12T/12, 10T/12, 12T/106 and 10T/106.
- polyamide 6/66, polyamide 6/612, polyamide 6/66/610, polyamide 6/66/12, polyamide 6/6T and polyamide 6/61 can be used according to the invention.
- Preferred amorphous or micro-crystalline homo- and copolyamides have the following compositions: PA 61, PA 61/6T, PA MXDI/61, PA MXDI/MXDT/61/6T, PA MXDI/121, PA MAC-MI/12, PA MACMI/MACMT/12, PA 61/MACMI/12, PA 61/6T/MACMI/MACMT/12, PA PACM6/11, PA PACM12, PA PACMI/PACM12, PA MACM6/11, PA MACM12, PA MACMI/MACM12, PA MACM12/PACM12, PA 61/6T/PACMI/PACMT/PACM12/612.
- Especially preferred polyamides for component (A) are PA6, PA11, PA12, PA610, PA612, PA1010, PA1012 and PA1212 or mixtures thereof.
- the polyamide elastomers (TPE-A) for component (B) can be prepared by insertion of flexible polyester, polyether or polyolefin segments in polyamide block polymers.
- the general structure is described in the book: Polyamid-Kunststoffhandbuch 3/4, Carl Hanser Verlag, Kunststoff 1998, pages 854 and 855.
- Polyester amides as they are described in EP-A-0 069 475, are prepared from ester-forming monomers and amide-forming monomers. From WO 85/02852 it could be taken that Polyester amides are prepared by reaction of a polyamide block with carboxyl groups at both chain ends and a polycaprolactonediol.
- EP 0 955 326 B1 relates to polyamides which are modified with dimerdiol and dimerdiol containing hydroxyl terminated polyester. The latter polyester amides are characterized by an excellent resistance to hydrolysis compared with other diol comprising polyamides.
- polyether amides The preparation of polyether amides is described for example in EP 0 459 862 B1 and CH 642 982.
- the polyether amides are thereby prepared starting from polyamide sequences, which have carboxyl groups at both chain ends, with polyoxyalkylene sequences, which have amino groups at both chain ends.
- JP 592 079 30 A describes the preparation of polyester ether amides, wherein the synthesis is carried out via cocondensation from polyamide blocks (e.g. PA 610 or PA 612), which have carboxyl groups at both chain ends, with polyether blocks, which are based on polyalkyleneoxide polyoles.
- polyamide blocks e.g. PA 610 or PA 612
- PA 610 or PA 612 polyamide blocks
- polyether blocks which are based on polyalkyleneoxide polyoles.
- Block copolyether ester ether amides are combinations of polyether amides and polyether ester amides. The synthesis takes place thereby via cocondensation from polyamide blocks, which have carboxyl groups at both chain ends, with both polyether dioles and polyether diamines.
- polyamide elastomers from the sub-groups of the polyether amides, the polyether ester amides and the block copolyether ester ether amides are preferred. These TPE-A are prepared from polyether blocks with reactive terminal groups, which are suitable for the formation of ester and/or amide bonds (hydroxyl and/or amino terminal groups are preferred).
- the polyether backbone may consist of polypropylene glycol (PPG), polytetramethyl glycol (PTMEG), polybutylene glycol (PBG), polyethylene glycol (PEG),
- PNPG Polyneopentyl glycol
- Grilon® ELX is a polyether amide with polyamide 6 hard blocks.
- Grilamid® ELY is a polyether amide with polyamide 12 hard blocks.
- a blend of polyamide 12 (component A) with a polyamide 6 polyether amide (component B) as well as an impact modifier, which acts as a compatibilizer, is used as material for the outer layer.
- a polyamide 12 with a polyamide 12 polyether amide or alternatively a polyamide 6 with a polyamide 12 polyether amide and optionally an impact modifier, which also can act as a compatibilizer, or a polyamide 6 with a polyamide 6 polyether amide, or mixtures thereof are used as mixture for the outer layer.
- the polyamide extrusion molding material according to the invention preferably comprises an impact modifier, which can act as a compatibilizer, wherein it is present in a portion within the range of from 0 to 35 wt.-%, referred to the weight of the total molding material. Especially favorable is a portion from 5 to 35 wt.-%, especially preferred a portion from 8 to 30 wt.-%, particularly preferred from 12 to 25 wt.-%.
- Elastomers or rubbers are suitable as impact modifiers. Such rubbers are amongst others described in EP 0 654 505 A1, from page 4, line 38, to page 5, line 58, and they are well-know to a person skilled in the art due to this detailed listing.
- Such impact modifiers share that they comprise elastomers and have at least a functional group which can react with the polyamide, for example a carboxylic acid or carboxylic acid anhydride group.
- impact modifiers takes place by means of grafting or copolymerising of the parent polymers with suitable reactive compounds such as maleic acid anhydride, (meth)acrylic acid or glycidyl(meth)acrylate. Therefore, impact modifiers can often be paraphrased as grafted copolyolefines. Also mixtures of different impact modifiers can be used.
- Impact modifiers can naturally also be comprised in the molding material of an inner layer which is based on polyamide.
- Preferred inner layer materials are corresponding to the inner layers of the already mentioned EP 1 452 307 A1 or GB 2 390 658 B.
- flame retardants pigments, stabilizers, reinforcements (e.g. glass fibers), plasticizers, mineral fillers such as kaolin or clay minerals (layer silicates), or particularly for the internal layer also additives to ensure electrical conductivity, i.e. antistatic additives (e.g. conductive carbon black or carbon fibers or graphite fibrils and carbon nanotubes, respectively) are suitable as further additives for the inner and/or outer layer.
- antistatic additives e.g. conductive carbon black or carbon fibers or graphite fibrils and carbon nanotubes, respectively
- these additives are preferably not more than 50 wt.-% of the entire molding material, wherein flame retardants can amount up to 15 wt.-%.
- the inner and/or outer layer comprises a plasticizer in a portion from 5 to 20 wt.-%, especially preferred in a portion from 10 to 15 wt.-%, related to the weight of the total molding material.
- An intermediate layer based on ethylene vinyl alcohol copolymer (EVOH) can be preferably used as a barrier layer on the inside of the outer layer according to the invention and/or between the outer and an optional inner layer.
- LCP liquid-crystalline polymers
- metal foils metal tubes or other barrier materials known to a person skilled in the art.
- These barrier layers may optionally be present with each other in different layers of the multi-layer composite.
- the multi-layer composite can also comprise still further intermediate layers, e.g. adhesion mediator layers.
- the barrier layer is based on ethylene vinyl alcohol copolymers (EVOH).
- EVOH ethylene vinyl alcohol copolymers
- Polyamides, which are suitable for the optional inner layer, are such, as already mentioned in the description of component (A).
- Polyamide or polymer mixtures are preferred which have inherent adhesion characteristics to the particularly preferred embodiment with a barrier layer of EVOH, as described in EP 1 452 307 A1 or EP 1 162 061 B1.
- More preferred polyamides are PA 6, PA 66, PA 610, PA 612 and mixtures thereof, and/or according to EP 1 452 307 Al a mixture of PA 6, PA 12 and a compatibilizer.
- the inner layer is formed of polyamide 610 or polyamide 612 or a mixture made of polyamide 610 and polyamide 6 and/or polyamide elastomers with polyamide 6 hard segments.
- the barrier layer preferably comprises at least 80 wt.-% ethylene vinyl alcohol copolymers (EVOH).
- EVOH ethylene vinyl alcohol copolymers
- the barrier layer based on ethylene vinyl alcohol copolymers (EVOH) comprises up to 20 wt.-% flexibilizing polymers, preferably copolyamide 6/12 and/or ethylene vinyl acetate copolymer (EVA).
- Such a further intermediate layer between the inner layer and/or the barrier layer can preferably consist of a material based on polyamide 6, based on copolymers like e.g. copolyamide 6/12, or based on a polyolefin, which is preferably functionalized, or mixtures thereof.
- an additional intermediate layer between the barrier layer, preferably consisting of ethylene vinyl alcohol copolymers, and the polyamide blend used as outer layer can be provided, said additional intermediate layer is selected from the same group of polymers as the optional internal intermediate layer.
- the barrier layer abuts directly on the outer layer. If the optional inner layer additionally abuts directly on the barrier layer, a particularly economical three-layer structure can be obtained, as already mentioned above.
- a further preferred embodiment of the invention is characterized in, that the optional inner layer or directly the barrier layer comprises electrically conductive additives.
- the optional inner layer or directly the barrier layer comprises electrically conductive additives.
- materials with electrically conductive additives For example carbon fibers or conductive carbon black, carbon black, graphite fibers, carbon nanotubes, metallic powder or fibers can be used as electrically conductive additives.
- Such additives are well-known to a person skilled in the art, in addition to the quantities, in which they are used.
- All possibly present layers of the multi-layer structure may have portions of further additives, such as plasticizers, pigments, impact modifiers (as already described above), heat and light stabilizers, reinforcements, compatibilizers, or mixtures thereof.
- further additives such as plasticizers, pigments, impact modifiers (as already described above), heat and light stabilizers, reinforcements, compatibilizers, or mixtures thereof.
- additives may be provided, which reduce permeation, like e.g. nano-fillers (layer silicates) or other mineral fillers.
- the multi-layer composite in form of a hollow section according to the invention has an outer diameter of 8 mm and a wall thickness of approx. 1 mm
- the inner layer has a thickness within the range of 0.25 to 0.45 mm
- the barrier layer of preferably EVOH has a thickness within the range of 0.10 to 0.3 mm
- the outer layer has a thickness within the range of 0.65 to 0.35 mm.
- the hollow section may at least in sections be corrugated and formed as a corrugated tube, respectively.
- the present invention concerns a method for the production of a multilayered hollow section, particularly a thermoplastic multi-layer composite, as described above.
- the optional inner layer, the barrier layer and the outer layer and optionally further intermediate layers between the barrier layer and the outer layer and/or the optional inner layer are joined during a preferably continuous process, more preferably to a tube and/or to a line, wherein optionally corrugations are additionally applied, optionally followed by a thermal shaping step.
- methods can be used such as coextrusion, coating, tandem extrusion or similar methods.
- the multi-layer tubes or hoses according to the invention can be used in the automotive sector as e.g. fuel tubes, brake air lines, compressed air lines, hydraulic lines, clutch lines and cooling lines.
- the polyamides have been prepared by methods known to a person skilled in the art.
- Ethylene vinyl alcohol copolymer was used as material for the barrier layer.
- EVOH Ethylene vinyl alcohol copolymer
- KURARAY is available under the name EVAL® under the product identification F101A and has an ethylene content of 32 mol %. It is available in Europe at the company EVAL Europe N.V. in Zwijindrecht, Belgium.
- a special acid-modified ethylene/ ⁇ -olefine copolymer namely an ethylene propylene copolymer grafted with maleic acid anhydride, was used as impact modifier, which can simultaneous act as a compatibilizer.
- Its MVR value (measured at 275° C./5 kg) was at 13 cm 3 /10 min, and its DSC melting point was at 55° C.
- BBSA n-butyl benzene sulfonamide
- Irganox 245 Commercial product of the company Ciba Speciality chemicals, Basel, Switzerland: Triethyleneglycol bis(3-(3′-tert-butyl-4′-hydroxy-5′-methylphenyl) propionate
- Hostanox® PAR24 Commercial product of the company Clariant, Basel, Switzerland: Tris(2,4-di-tert-butylphenyl) phosphate.
- a master batch based of polyamide 12 with 30 wt.-% carbon nano-tube was used as conductivity additive.
- This product is a commercial product of the company Hyperion Catalysis Inc.
- the molding materials indicated in the following table 2 for the outer layer were manufactured at temperatures between 240 and 300° C. on a two screw kneading machine ZSK30 of the company Werner und Pfleiderer. Polymers, impact modifier, plasticizers and stabilizers were charged into the feeder of the extruder. In each case a mixture of Irganox® 245 with 0.7 wt.-% and Hostanox® PAR24 with 0.3 wt.-%, related to 100 wt.-% compound (total molding material) were used as stabilizers.
- the molding materials (inner layer), indicated in the following table 3, were manufactured at temperatures between 240 and 300° C. on a two screw kneading machine ZSK25 of the company Werner und Pfleiderer. Polymers, compatibilizer, plasticizers and stabilizers were charged into the feeder of the extruder.
- the antistatic molding materials (inner layer), indicated in the following table 4, were manufactured at temperatures between 240 and 300° C. on a two screw kneading machine ZSK25 of the company Werner and Pfleiderer. Polymers, compatibilizers, carbon nanotube masterbatch, plasticizers and stabilizers were charged into the introduction of the extruder.
- Tubes and lines, respectively, according to the layer structures described in table 5 were manufactured in a coextrusion process on a usual tube extrusion apparatus, wherein the individual layers were extruded essentially at the same time as a multi-layer composite.
- the coextrusion process becomes particularly simple if the line exhibits only three layers.
- the described tubing assemblies B1 and VB1 were manufactured by the coextrusion process at different withdrawal speeds (extrusion speeds) and appropriate material throughputs.
- the elongation at break was determined at the manufactured multi-layer tubes according to the following specification: Elongation at break according to DIN EN ISO 527-2 (according to standard Volkswagen specification TL 524 35).
- the elongation at break ⁇ R is the elongation at the moment at break.
- test results of table 6 show in a convincing way, how the quality of the respective multi-layer composites can be significantly improved with the present invention, i.e. the respective outer layer composition, and how the productivity and/or the output of an extrusion apparatus can thereby additionally be enormously increased.
- the invention allows a large increase of economic efficiency during the production of multi-layer tubes.
- Zinc chloride test Test according to SAE J2260 paragraph 7.5, resistance to zinc chloride, respective Ford WSS-M 98D33-A3 paragraph 3.4.5, resistance to zinc chloride.
- Sour gas test Test according to SAE J2260 paragraph 7.8, auto-oxidised gasoline (cold impact ( ⁇ 40° C.) after storage PN90 1000 h at 40° C.).
- test medium FAM B (72 h/60° C.).
- the test medium FAM B must not contain flocculation or turbidity after storage.
- the table 7 illustrates that examples 2-9 successfully pass all tests and thus are also set apart from the solutions known in the state of the art by the resistance to elution as well as the resistance to sour gas.
Abstract
Description
- The present patent application claims priority of European patent application EP 06 015 922.5 and relates to modified polyamide (PA) extrusion molding materials modified with polyamide elastomers (TPE-A) for the improvement of the elongation at break of the extruded article at higher extrusion speed. The invention further relates to multi-layer composites, in particular to thermoplastic multi-layer composites, in form of hollow sections, preferably for the automotive sector, comprising at least one outer layer made from these molding materials as well as at least a further layer, preferably a barrier layer and optionally further layers. The present invention relates also to a method for the production of said hollow sections, which may especially exist in the form of tubes, pipes or hoses, preferably for the automotive sector, more preferably as fuel tube or pipe for liquid fuels such as gasoline or diesel or for alternative fuels like e.g. bio ethanol (and appropriate fuel mixtures) or rape methyl esters.
- Conversion operations and in particular extrusion methods for plastics are for a long time state of the art and are e.g. described in the book: W. Michaeli, Einführung in die Kunststoffverarbeitung, 4. Edition 1999, Carl Hanser Verlag Munich, page 85 ff. In FIG. 6.1.1 on page 85 the conceptional diagram of a tube extrusion apparatus is described. With extrusion speed the speed of the caterpillar take-off and the speed of the prepared hollow section transported thereby is meant, respectively, thus the production speed of the extrusion apparatus.
- During the production of multi-layer tubes or hoses having a polyamide outer layer by means of extrusion it was found that the mechanical characteristics, like elongation at break and cold impact strength, are worsening, if the extrusion equipment is operated with higher speed (starting from 20 m/min, increasing to e.g. 60 to 80 m/min or higher). In the present connection, the drawdown speed of the caterpillar take-off after the cooling line and the calibration (which may be accomplished e.g. by means of water cooling) is meant with the extrusion speed. In addition, it is to be noticed that when operating the apparatus at a higher extrusion speed also the material output of the extruder must be of course adjusted proportionally higher at the same time, because even on the higher speed level a certain article with the same cross section and the same wall thickness and to the same diameter respectively shall still result. Thus, during the evaluation of the mechanical characteristics in the present case extruded articles of the same geometry are respectively compared.
- The above specified effect, that at higher extrusion speeds the mechanical characteristics of the manufactured articles are worsening, is already known to experts for a long time and represents a disadvantage, because the extrusion speed is limited thereby. The critical point of the multi-layer tube is namely the outer surface, i.e. the surface section of the tube, which cools down most quickly from the outer and which orients itself more distinctly at higher speed. Consequently, due to the higher tension in the outer surface and the smaller elasticity when mechanically loaded, respectively, it begins to break earlier. The effect mentioned above is described by e.g. A. Carin et al. in Intern. Polymer Processing XX (2005), pages 305-311. Here one finds on page 310 the well-known relation that the orientation of the outer surface increases with increasing drawdown speed, i.e. the elongation at break decreases vice versa.
- According to EP 0 245 125 B1, it has been tried to get the orientation in the outer surface to disappear by a complicated and not completely harmless subsequent treatment method i.e. by means of flaming calibrated tubes with following renewed cooling.
- EP 1 452 307 A1 describes multi-layer automotive tubes, which are resistant to peroxide containing gasoline and which also comply to the usual requirements regarding cold impact and which have a simple and economical structure. The multi-layer tube is formed with an inner layer based on a mixture of polyamide homopolymers, and it additionally has a compatibilizer. The characteristic feature of EP 1 452 307 A1 is the fact that the inner layer is not formed based on only one polyamide homopolymer or based on a mixture of polyamide 6 copolymers, but from a blend of different non-mixable polyamide homopolymers, using a compatibilizer. If this blend is also used for the outer layer of a multi-layer line, as provided in EP 1,452,307 A1, the above mentioned effect also arises, that with increasing extrusion speed the elongation at break of the multi-layer tube is reduced.
- GB 2 390 658 B describes multi-layer polymer tube or hose lines with an ethylene/vinyl alcohol copolymer (abbreviated EVAL or, in the English-speaking world, also designated as EVOH) barrier layer as well as with an outer layer of polyamide 612 or polyamide 610 and an inner layer of polyamide 6, polyamide 612 or polyamide 610. These above mentioned materials have a very good dimensional stability under heat and good barrier characteristics against hydrocarbons and have additionally good adhesion between the layers, i.e. the multi-layer tube is resistant against delamination. But even with these multi-layer tubes the well-known effect arises that the elongation at break is reduced at increasing extrusion speed.
- DE 698 31 239 T2 describes multilayered structures based on polyamides, in particular tubes with multilayered structure, wherein at least one inner layer and at least one outer layer are provided. The outer layer is formed from a mixture of at least one copolyamide of the type 6/6-36 and at least a second thermoplastic polymer, i.e. of the type polyamide 6. The second polymer does not contain plasticizers or elastomers.
- EP-A-1 559 537 describes a multilayered plastic tube with barrier characteristics for automobiles. The plastic of the substrate may consist of a blend of polyamides. Further, a barrier layer made of EVOH is provided. The outer layer of the multilayered fuel tube can additionally have a jacket by an outer protective layer, which consists of a thermoplastic elastomer (TP) and a thermoplastic polyurethane (TPU), respectively. This additional protective layer can be coextruded with the other layers and thereby becomes a component of the composite composite.
- US 2002/0012806 A1 describes thermoplastic multilayered structures, which include inner layers made from polyamides or polyamide mixtures. The polymer mixtures can contain usual polyamide types without plasticizers.
- EP 0 710 537 A2 describes a multilayered line or conduit, wherein the inner layer consists of polyamides and which outer layer consists of polyamides having a layer of EVOH disposed between. The mixtures of the layer materials do not contain plasticizers and/or polyamide elastomers.
- DE 35 10 395 A1 describes multi-layer fuel tubes or hose lines with an alcohol barrier layer based on polyvinyl alcohol. In the direction to the inner flow channel a polyamide protective layer made of polyamide 11 or 12 is provided.
- U.S. Pat. No. 5,960,977 A1 describes polymer hoses or tubes with corrugated segments.
- Use of elastomer modified polymers has further become known in other areas of the state of the art e.g. in medical technology or with fiber-optic cables. DE 3 724 997 C2 describes the use of polyamide/polyamide elastomer mixtures in the production of polymer protective layers of fiber-optic cables. The coating of fiber-optic cables with a layer of polyamide/polyamide elastomer mixtures is accomplished according to DE 3 724 997 C2 using the extrusion method.
- EP 0 566 755 B 1 further describes polyether amide hoses for medical instruments, which are extruded from a mixture of two polymers, of which one polymer is a polyether amide and the other one is a polyether ester amide or a polyamide.
- DE 2 716 004 C3 describes mixable polyether ester amides based on laurinlactam with polyamide 12 for the production of flexible, cool impact mono tubes.
- In DE 3 724 997 C2 and DE 2 716 004 C3 as well as in EP 0 566 755 B1 polyether amides with laurinlactam are used as monomer for the polyamide block. Appropriate modified mixtures with polyamide 12 are also mentioned in the book: Polyamid-Kunststoffhandbuch, 3/4, 1998, Carl Hanser Verlag, page 872, paragraph 8.3.3. These blends are showing a partial compatibility, which is based on the cocrystallization of the polyamide 12 blocks with the homopolyamide. In the three corresponding patents neither multi-layer conduits nor the compatibilization are mentioned. However, such a mixture would not adhere on barrier materials, in particular not on EVOH. Polyamides which cause adhesion to EVOH, are described for example in the EP 1 162 061 B1.
- DE 3 916 001 A1 describes a four-component mixture of amorphous copolyamides, block polyether polyamides, block polyether ester polyamides and modified copolyolefines. The disadvantage of such mixtures, which contain amorphous copolyamides, is the lower resistance to chemicals, especially to zinc chloride, which must be achieved for fuel lines.
- Therefore, it is an object of the present invention to provide a thermoplastic multi-layer composite, which is improved with regard to the layer adhesion and the resistance regarding resistance to chemicals, permeation as well as resistance to elution, wherein even at higher extrusion speeds only small tensions in the outer surface are to be found, e.g. the mechanical characteristics are not impaired, and the economy of the tubing production can be substantially increased.
- The inventors have now surprisingly found during extrusion experiments of multi-layer tubes, particularly with barrier layers, as e.g. from EVOH (ethylene vinyl alcohol copolymers), that the effect of impairment of the mechanical characteristics in the outer surface can be inverted in a completely unexpected way, if one adds a certain portion of polyamide elastomer to the polyamide molding material provided for the outer layer, in particular if the polyamide elastomer is not mixable with the polyamide.
- Therefore, the invention relates to new multi-layer composites, especially to thermoplastic multi-layer composites, in form of an extruded hollow section, comprising a thermoplastic outer layer and at least one further layer, wherein the outer layer is formed of a mixture based on (A) 80 to 20 parts by weight of at least one polyamide (PA) and (B) 20 to 80 parts by weight of at least one polyamide elastomer (TPE-A), the latter from the group of the polyether amides, the polyester amides, the polyether ester amides, the polyether ester ether amides and mixtures thereof, wherein the sum of (A) and (B) results in 100 parts by weight. The hollow sections with such an outer layer manufactured at higher extrusion speed (particularly over 20 m/min) showing a higher elongation at break, compared to an otherwise identical hollow section, manufactured at lower extrusion speed, as well as particularly also compared with a hollow section with a polyamide outer layer without polyamide elastomer additive, manufactured at the same extrusion speed, wherein the elongation at break is determined on the finished hollow section according to DIN EN ISO 527-2. In other words this means that faster produced multi-layer tubes with an outer layer according to the invention exhibit a higher elongation at break compared with multi-layer tubes manufactured at lower extrusion speeds.
- If one adds a PA elastomer portion (TPE-A) to the outer layer material, i.e. a polyamide (PA), e.g. 50 parts by weight, related to 100 parts by weight from the sum of PA and TPE-A, already at 20 m/min extrusion speed the elongation at break εR begins to reach a value of over 200%, in contrast to a multi-layer composite with polyamide outer layer without (TPE-A)-additive and even increases at higher speed (see experiments of table 4 with 40 m/min and 60 m/min), which is particularly amazing. The definition of the elongation at break εR is well-known to a skilled person and can be found e.g. in the book: Kunststoff-Kompendium, 2. Edition, VOGEL Buchverlag Würzburg, 1988, page 239 among the characteristic values.
- Thus, both the quality and the productivity of the extrusion of the multi-layer composites, in particular of multi-layer tubes, can be enormously increased according to the invention.
- As polyamide (PA) for the component (A) favorably polycondensation products of aliphatic lactams or ω-aminocarboxylic acids with 4 to 44 carbon atoms, preferably 4 to 18 carbon atoms, or such from aromatic aminocarboxylic acids with 6 to 20 carbon atoms are used.
- Likewise suitably are polycondensation products from at least one diamine and at least one dicarboxylic acid with 2 to 44 carbon atoms, respectively. Examples of such diamines are ethylene diamine, 1,4-diamino butane, 1,6-diamino hexane, 1,10-diamino decane, 1,12-diamino dodecane, m- and p-xylylene diamine, cyclohexyl dimethylene amine, bis-(aminocyclohexyle)methane and its alkyl derivatives.
- Examples of dicarboxylic acids are succinic, glutaric, adipic, pimelic, suberic, azelaic and sebacic acid, dodecanic diacid, dimer fatty acids with 36 or 44 C-atoms, 1,6-cyclohexane dicarboxylic acid, terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid.
- Especially preferred polyamides (PA) for component (A) are homo- and copolyamides based on PA6, PA11, PA46, PA12, PA1212, PA1012, PA610, PA612, PA69, PA6T, PA6I, PA10T, PA12T, PA12I, their mixtures or copolymers based on these polyamides, wherein PA11, PA12, PA1212, PA10T, PA12T are preferred. Also preferred are copolymers based on the above mentioned polyamides, like e.g. 12T/12, 10T/12, 12T/106 and 10T/106. Further, also polyamide 6/66, polyamide 6/612, polyamide 6/66/610, polyamide 6/66/12, polyamide 6/6T and polyamide 6/61 can be used according to the invention.
- Preferred amorphous or micro-crystalline homo- and copolyamides have the following compositions: PA 61, PA 61/6T, PA MXDI/61, PA MXDI/MXDT/61/6T, PA MXDI/121, PA MAC-MI/12, PA MACMI/MACMT/12, PA 61/MACMI/12, PA 61/6T/MACMI/MACMT/12, PA PACM6/11, PA PACM12, PA PACMI/PACM12, PA MACM6/11, PA MACM12, PA MACMI/MACM12, PA MACM12/PACM12, PA 61/6T/PACMI/PACMT/PACM12/612.
- Especially preferred polyamides for component (A) are PA6, PA11, PA12, PA610, PA612, PA1010, PA1012 and PA1212 or mixtures thereof.
- The polyamide elastomers (TPE-A) for component (B) can be prepared by insertion of flexible polyester, polyether or polyolefin segments in polyamide block polymers. The general structure is described in the book: Polyamid-Kunststoffhandbuch 3/4, Carl Hanser Verlag, Munich 1998, pages 854 and 855.
- Polyester amides, as they are described in EP-A-0 069 475, are prepared from ester-forming monomers and amide-forming monomers. From WO 85/02852 it could be taken that Polyester amides are prepared by reaction of a polyamide block with carboxyl groups at both chain ends and a polycaprolactonediol. EP 0 955 326 B1 relates to polyamides which are modified with dimerdiol and dimerdiol containing hydroxyl terminated polyester. The latter polyester amides are characterized by an excellent resistance to hydrolysis compared with other diol comprising polyamides.
- The preparation of polyether amides is described for example in EP 0 459 862 B1 and CH 642 982. The polyether amides are thereby prepared starting from polyamide sequences, which have carboxyl groups at both chain ends, with polyoxyalkylene sequences, which have amino groups at both chain ends.
- JP 592 079 30 A describes the preparation of polyester ether amides, wherein the synthesis is carried out via cocondensation from polyamide blocks (e.g. PA 610 or PA 612), which have carboxyl groups at both chain ends, with polyether blocks, which are based on polyalkyleneoxide polyoles.
- Further examples of usable TPE-A according to the present invention can be found in the book: Polyamid Kunststoffhandbuch, 3/4, 1998, Carl Hanser Verlag, pages 854-871.
- Block copolyether ester ether amides, as mentioned in EP 0 399 415 B1 and U.S. Pat. No. 5,574,128, respectively, are combinations of polyether amides and polyether ester amides. The synthesis takes place thereby via cocondensation from polyamide blocks, which have carboxyl groups at both chain ends, with both polyether dioles and polyether diamines.
- For component (B) polyamide elastomers (TPE-A) from the sub-groups of the polyether amides, the polyether ester amides and the block copolyether ester ether amides are preferred. These TPE-A are prepared from polyether blocks with reactive terminal groups, which are suitable for the formation of ester and/or amide bonds (hydroxyl and/or amino terminal groups are preferred). The polyether backbone may consist of polypropylene glycol (PPG), polytetramethyl glycol (PTMEG), polybutylene glycol (PBG), polyethylene glycol (PEG),
- Polyneopentyl glycol (PNPG) and/or their mixtures and/or their copolymers and/or their block polymers.
- Commercial products of typical polyether amides or of polyether ester amides are to be found in the book: Polyamid Kunststoffhandbuch, 3/4, 1998, Carl Hanser Verlag, page 875. Exemplary materials are the products Grilon® ELX or Grilamid® ELY obtainable from EMS-Chemie AG, Domat/Ems, Switzerland. Grilon® ELX is a polyether amide with polyamide 6 hard blocks. The product Grilamid® ELY is a polyether amide with polyamide 12 hard blocks.
- According to a particularly preferred embodiment of the invention a blend of polyamide 12 (component A) with a polyamide 6 polyether amide (component B) as well as an impact modifier, which acts as a compatibilizer, is used as material for the outer layer. As alternative preferred variants a polyamide 12 with a polyamide 12 polyether amide or alternatively a polyamide 6 with a polyamide 12 polyether amide and optionally an impact modifier, which also can act as a compatibilizer, or a polyamide 6 with a polyamide 6 polyether amide, or mixtures thereof are used as mixture for the outer layer.
- The polyamide extrusion molding material according to the invention preferably comprises an impact modifier, which can act as a compatibilizer, wherein it is present in a portion within the range of from 0 to 35 wt.-%, referred to the weight of the total molding material. Especially favorable is a portion from 5 to 35 wt.-%, especially preferred a portion from 8 to 30 wt.-%, particularly preferred from 12 to 25 wt.-%. Elastomers or rubbers are suitable as impact modifiers. Such rubbers are amongst others described in EP 0 654 505 A1, from page 4, line 38, to page 5, line 58, and they are well-know to a person skilled in the art due to this detailed listing. Such impact modifiers share that they comprise elastomers and have at least a functional group which can react with the polyamide, for example a carboxylic acid or carboxylic acid anhydride group.
- The preparation of impact modifiers takes place by means of grafting or copolymerising of the parent polymers with suitable reactive compounds such as maleic acid anhydride, (meth)acrylic acid or glycidyl(meth)acrylate. Therefore, impact modifiers can often be paraphrased as grafted copolyolefines. Also mixtures of different impact modifiers can be used.
- Impact modifiers can naturally also be comprised in the molding material of an inner layer which is based on polyamide. Preferred inner layer materials are corresponding to the inner layers of the already mentioned EP 1 452 307 A1 or GB 2 390 658 B.
- Additionally, flame retardants, pigments, stabilizers, reinforcements (e.g. glass fibers), plasticizers, mineral fillers such as kaolin or clay minerals (layer silicates), or particularly for the internal layer also additives to ensure electrical conductivity, i.e. antistatic additives (e.g. conductive carbon black or carbon fibers or graphite fibrils and carbon nanotubes, respectively) are suitable as further additives for the inner and/or outer layer. However, these additives are preferably not more than 50 wt.-% of the entire molding material, wherein flame retardants can amount up to 15 wt.-%. In preferred embodiments the inner and/or outer layer comprises a plasticizer in a portion from 5 to 20 wt.-%, especially preferred in a portion from 10 to 15 wt.-%, related to the weight of the total molding material.
- An intermediate layer based on ethylene vinyl alcohol copolymer (EVOH) can be preferably used as a barrier layer on the inside of the outer layer according to the invention and/or between the outer and an optional inner layer. Additionally, it is also possible to use barrier layers based on fluoro polymers or copolymers of fluoro polymers, polyphenylene sulfides, partly aromatic polyesters like e.g. PBT or PEN, partly aromatic polyamides, such as polyphthalamides or polyamides based on MXDA, liquid-crystalline polymers (LCP), metal foils, metal tubes or other barrier materials known to a person skilled in the art. These barrier layers may optionally be present with each other in different layers of the multi-layer composite. Naturally, the multi-layer composite can also comprise still further intermediate layers, e.g. adhesion mediator layers.
- All mentioned polymers or metals, which are suitable for the barrier layer, are rather rigid materials, why it is particularly preferred to obtain a multi-layer composite with good composite adhesion between the individual layers, which has a high elongation at break in its total combination for the further processing steps after the extrusion process, in particular for the thermal form process.
- In a particularly preferred embodiment the barrier layer is based on ethylene vinyl alcohol copolymers (EVOH). In a further preferred embodiment it is possible to let the optional inner layer abut directly on the barrier layer. Polyamides, which are suitable for the optional inner layer, are such, as already mentioned in the description of component (A). Polyamide or polymer mixtures are preferred which have inherent adhesion characteristics to the particularly preferred embodiment with a barrier layer of EVOH, as described in EP 1 452 307 A1 or EP 1 162 061 B1. More preferred polyamides are PA 6, PA 66, PA 610, PA 612 and mixtures thereof, and/or according to EP 1 452 307 Al a mixture of PA 6, PA 12 and a compatibilizer. Most preferably the inner layer is formed of polyamide 610 or polyamide 612 or a mixture made of polyamide 610 and polyamide 6 and/or polyamide elastomers with polyamide 6 hard segments.
- In case of a barrier layer based on ethylene vinyl alcohol copolymers (EVOH) the barrier layer preferably comprises at least 80 wt.-% ethylene vinyl alcohol copolymers (EVOH). To increase the stress crack stability for extreme strains it is advantageous, if the barrier layer based on ethylene vinyl alcohol copolymers (EVOH) comprises up to 20 wt.-% flexibilizing polymers, preferably copolyamide 6/12 and/or ethylene vinyl acetate copolymer (EVA).
- It is also possible to provide further layers between the inner layer and/or the barrier layer. Such a further intermediate layer between the inner layer and a barrier layer preferably formed of ethylene vinyl alcohol copolymers can preferably consist of a material based on polyamide 6, based on copolymers like e.g. copolyamide 6/12, or based on a polyolefin, which is preferably functionalized, or mixtures thereof. Further, an additional intermediate layer between the barrier layer, preferably consisting of ethylene vinyl alcohol copolymers, and the polyamide blend used as outer layer can be provided, said additional intermediate layer is selected from the same group of polymers as the optional internal intermediate layer.
- According to a particularly preferred embodiment the barrier layer abuts directly on the outer layer. If the optional inner layer additionally abuts directly on the barrier layer, a particularly economical three-layer structure can be obtained, as already mentioned above.
- A further preferred embodiment of the invention is characterized in, that the optional inner layer or directly the barrier layer comprises electrically conductive additives. In addition, it is possible to provide a still further most internal layer at the internal layer, made from materials with electrically conductive additives. For example carbon fibers or conductive carbon black, carbon black, graphite fibers, carbon nanotubes, metallic powder or fibers can be used as electrically conductive additives. Such additives are well-known to a person skilled in the art, in addition to the quantities, in which they are used.
- All possibly present layers of the multi-layer structure may have portions of further additives, such as plasticizers, pigments, impact modifiers (as already described above), heat and light stabilizers, reinforcements, compatibilizers, or mixtures thereof.
- Further, additives may be provided, which reduce permeation, like e.g. nano-fillers (layer silicates) or other mineral fillers.
- Typically, the multi-layer composite in form of a hollow section according to the invention, as for example a fuel tube, has an outer diameter of 8 mm and a wall thickness of approx. 1 mm, the inner layer has a thickness within the range of 0.25 to 0.45 mm, the barrier layer of preferably EVOH has a thickness within the range of 0.10 to 0.3 mm and the outer layer has a thickness within the range of 0.65 to 0.35 mm. The hollow section may at least in sections be corrugated and formed as a corrugated tube, respectively.
- Further, the present invention concerns a method for the production of a multilayered hollow section, particularly a thermoplastic multi-layer composite, as described above. Thereby, the optional inner layer, the barrier layer and the outer layer and optionally further intermediate layers between the barrier layer and the outer layer and/or the optional inner layer are joined during a preferably continuous process, more preferably to a tube and/or to a line, wherein optionally corrugations are additionally applied, optionally followed by a thermal shaping step. Therein, methods can be used such as coextrusion, coating, tandem extrusion or similar methods.
- The multi-layer tubes or hoses according to the invention can be used in the automotive sector as e.g. fuel tubes, brake air lines, compressed air lines, hydraulic lines, clutch lines and cooling lines.
- The invention will now be described in more detail based on the following examples, but without limiting same.
-
TABLE 1 Used polyamide and polyamide elastomers Type of polyamide description Grilamid ® L25*) very viscous polyamide 12 Grilamid ® L16*) medium viscous polyamide 12 Grilon ® F34*) medium viscous polyamide 6 Grilon ® XE 3871*) polyether amide with PA 6 hard blocks Grilamid ® XE 3908*) medium viscous PA612 Grilamid ® XE 1306*) medium viscous PA610 Grilamid ® XE 3928*) medium viscous PA610
*)Commercial products of the company EMS-CHEMIE AG, Domat/EMS, Switzerland
- Used materials:
- Polyamides and Polyamide Elastomers:
- The polyamides have been prepared by methods known to a person skilled in the art.
- Ethylene Vinyl Alcohol Copolymer (EVOH):
- Ethylene vinyl alcohol copolymer (EVOH) was used as material for the barrier layer. In the illustrative embodiments it is a product of the company KURARAY, which is available under the name EVAL® under the product identification F101A and has an ethylene content of 32 mol %. It is available in Europe at the company EVAL Europe N.V. in Zwijindrecht, Belgium.
- Impact Modifier:
- According to the invention a special acid-modified ethylene/α-olefine copolymer, namely an ethylene propylene copolymer grafted with maleic acid anhydride, was used as impact modifier, which can simultaneous act as a compatibilizer. Its MVR value (measured at 275° C./5 kg) was at 13 cm3/10 min, and its DSC melting point was at 55° C.
- Plasticizer:
- BBSA (n-butyl benzene sulfonamide) was used as plasticizer.
- Stabilizers:
- Irganox 245: Commercial product of the company Ciba Speciality chemicals, Basel, Switzerland: Triethyleneglycol bis(3-(3′-tert-butyl-4′-hydroxy-5′-methylphenyl) propionate Hostanox® PAR24: Commercial product of the company Clariant, Basel, Switzerland: Tris(2,4-di-tert-butylphenyl) phosphate.
- Conductivity Additives:
- A master batch based of polyamide 12 with 30 wt.-% carbon nano-tube was used as conductivity additive. This product is a commercial product of the company Hyperion Catalysis Inc.
- The molding materials indicated in the following table 2 for the outer layer were manufactured at temperatures between 240 and 300° C. on a two screw kneading machine ZSK30 of the company Werner und Pfleiderer. Polymers, impact modifier, plasticizers and stabilizers were charged into the feeder of the extruder. In each case a mixture of Irganox® 245 with 0.7 wt.-% and Hostanox® PAR24 with 0.3 wt.-%, related to 100 wt.-% compound (total molding material) were used as stabilizers.
TABLE 2 Molding materials for the outer layer components unit FE8072 Z6509 Z7844 Z8262 Z8263 Grilamid L25 wt.-% 42 42.5 39.5 39.125 — Grilamid L16 wt.-% — — — — 39.125 Grilon F34 wt.-% 42 42.5 — — — Grilon XE wt.-% — — 39.5 39.125 39.125 3871 Impact wt.-% 15 15 20 20 20 modifier Stabilizer wt.-% 1 — 1 1 1 mixture Black wt.-% — — — 0.75 0.75 master batch - The molding materials (inner layer), indicated in the following table 3, were manufactured at temperatures between 240 and 300° C. on a two screw kneading machine ZSK25 of the company Werner und Pfleiderer. Polymers, compatibilizer, plasticizers and stabilizers were charged into the feeder of the extruder.
TABLE 3 Non-antistatic molding materials for the inner layer components unit W6994 Z7837 Z7838 Z7839 Z7873 Z8312 W9874 Grilamid L25 wt.-% — — — — 39 — — Grilamid XE 1306 wt.-% — — — — — 69.5 58.5 Grilamid XE 3928 wt.-% — 83 90 — — — — Grilamid XE 3908 wt.-% — — — 90 — — — Grilon F34 wt.-% 83 — — — 39 — 5 Grilamid XE 3871 wt.-% — — — — — — 5 impact modifier wt.-% 10 10 10 10 15 20 20 plasticizer wt.-% 7 7 — — 6 10 11 stabilizer wt.-% — — — — 1 0.5 0.5 - The antistatic molding materials (inner layer), indicated in the following table 4, were manufactured at temperatures between 240 and 300° C. on a two screw kneading machine ZSK25 of the company Werner and Pfleiderer. Polymers, compatibilizers, carbon nanotube masterbatch, plasticizers and stabilizers were charged into the introduction of the extruder.
TABLE 4 antistatic molding materials for the inner layer components unit PA6/PA12 ESD PA610 W ESD Grilamid L25 wt.-% 27.5 — Grilon F34 wt.-% 27.5 — Grilamid XE 3928 wt.-% — 48 plasticizer wt.-% — 7 compatibilizer wt.-% 15 15 conductivity additive wt.-% 30 30 - Tubes and lines, respectively, according to the layer structures described in table 5 were manufactured in a coextrusion process on a usual tube extrusion apparatus, wherein the individual layers were extruded essentially at the same time as a multi-layer composite. The coextrusion process becomes particularly simple if the line exhibits only three layers.
- In the following table 5 the layer structures B1-B9 according to the invention, as well as the layer structures serving as comparative examples according to the state of the art) VB1-VB4 are shown:
TABLE 5 Layer structures Pipes 8 * 1 mm (8 mm outer diameter, 1 mm wall thickness) inner layer intermediate layer barrier layer outer layer VB1 Z7873 — EVOH FE8072 VB2 W6994 — EVOH Z6509 VB3 Z6509 — EVOH Z6509 VB4 PA6/PA12 ESD W6994 EVOH Z6509 B1 Z7873 — EVOH Z7844 B2 Z7837 — EVOH Z6509 B3 Z7838 — EVOH Z6509 B4 Z7839 — EVOH Z6509 B5 PA610 W ESD W6994 EVOH Z6509 B6 PA610 W ESD Z7838 EVOH Z6509 B7 Z8312 — EVOH Z8262 B8 Z8312 — EVOH Z8263 B9 W9874 — EVOH Z8263 - The described tubing assemblies B1 and VB1 were manufactured by the coextrusion process at different withdrawal speeds (extrusion speeds) and appropriate material throughputs. The elongation at break was determined at the manufactured multi-layer tubes according to the following specification: Elongation at break according to DIN EN ISO 527-2 (according to standard Volkswagen specification TL 524 35). The elongation ε is the length variation ΔL=L−L0 in mm, related to the original measuring length L0 in
and is expressed as percentage (see already quoted Kunststoff-Komendium, Vogel-Verlag, 1988, page 239 “characteristic values”). The elongation at break εR is the elongation at the moment at break. - In the following table 6 the withdrawal speeds during the tube extrusion and the results of the elongation at break measurement are shown.
TABLE 6 Elongation at break as a function of the withdrawal speed Pipes 8 * 1 mm (8 mm outer diameter, 1 mm wall thickness) withdrawal speed [m/min] elongation at break [%] VB1 20 165 VB1 40 130 VB1 60 110 B1 20 210 B1 40 230 B1 60 250 - The obtained results of the comparative examples already show at an extrusion speed of 20 m/min that the elongation at break specification according to VOLKSWAGEN TL 524 35, in which an elongation at break of >200% is required, is not reached. However, all examples according to the invention fulfill this requirement, even without problems at increased speeds.
- By the way, all comparative examples and examples according to the invention pass the cold impact test according to VOLKSWAGEN TL 524 35.
- The test results of table 6 show in a convincing way, how the quality of the respective multi-layer composites can be significantly improved with the present invention, i.e. the respective outer layer composition, and how the productivity and/or the output of an extrusion apparatus can thereby additionally be enormously increased. Thus, the invention allows a large increase of economic efficiency during the production of multi-layer tubes.
- The following tests were accomplished at the tubing assemblies B2-B9 and VB2-VB4 described in table 5:
- Cold impact test according to SAE J2260 paragraph 7.5 as well as bursting pressure according to paragraph 7.1.
- Zinc chloride test: Test according to SAE J2260 paragraph 7.5, resistance to zinc chloride, respective Ford WSS-M 98D33-A3 paragraph 3.4.5, resistance to zinc chloride. Sour gas test: Test according to SAE J2260 paragraph 7.8, auto-oxidised gasoline (cold impact (−40° C.) after storage PN90 1000 h at 40° C.).
- Resistance to elution: Test according to VOLKSWAGEN TL52435, paragraph 6.
- Examination of the resistance to elution of a multi-layer tube after storage FAM B (72 h/60° C.). The test medium FAM B must not contain flocculation or turbidity after storage.
- In the following table 7 the results of the cold impact tests, sour gas tests, zinc chloride tests and the resistance to elution are illustrated. +means that the test has been passed, −stands for failure in the test.
TABLE 7 Test results Pipes 8 * 1 mm (8 mm outer diameter, 1 mm wall thickness) cold impact SAE SAE [% breakage], resistance to resistance to resistance to 0% required ZnCl2 sour gas elution VB2 − − − − VB3 + + + − VB4 + + + − B2 + + + + B3 + + + + B4 + + + + B5 + + + + B6 + + + + B7 + + + + B8 + + + + B9 + + + + - The table 7 illustrates that examples 2-9 successfully pass all tests and thus are also set apart from the solutions known in the state of the art by the resistance to elution as well as the resistance to sour gas.
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CN109849371A (en) * | 2019-03-27 | 2019-06-07 | 成都联科航空技术有限公司 | The variable cross-section hollow structure composite material parts forming method of high-precision inner surface |
CN111117217A (en) * | 2019-12-26 | 2020-05-08 | 上海普利特复合材料股份有限公司 | Nylon material for injection molding of low-permeability fuel tank and preparation method thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5284184A (en) * | 1992-04-14 | 1994-02-08 | Itt Corporation | Corrugated multi-layer tubing having at least one fluoroplastic layer |
US5960977A (en) * | 1998-05-14 | 1999-10-05 | Itt Manufacturing Enterprises, Inc. | Corrugated polymeric filler neck tubing |
US6162244A (en) * | 1996-03-29 | 2000-12-19 | Willy Ruesch Ag | Layered stent |
US20020012806A1 (en) * | 2000-06-09 | 2002-01-31 | Ems-Chemie Ag | Thermoplastic multilayer composites |
US20050025920A1 (en) * | 2003-02-28 | 2005-02-03 | Alex Stolarz | Thermoplastic multilayer composite in the form of a hollow body |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH655941A5 (en) * | 1982-08-30 | 1986-05-30 | Inventa Ag | Flexible, polyamide-based thermoplastic moulding compositions with good low-temperature impact strength |
DE3510395A1 (en) | 1985-03-22 | 1986-09-25 | Technoform Caprano + Brunnhofer KG, 3501 Fuldabrück | Fuel-carrying line which can be installed fixed with a predetermined length for a motor vehicle |
DE69525415T2 (en) | 1994-11-04 | 2002-06-20 | Sumitomo Electric Industries | Shrinkable tube, made of composite material, and method of sealing using this tube |
FR2739388B1 (en) * | 1995-09-29 | 1997-11-21 | Nyltech Italia | THERMOPLASTIC COMPOSITION FOR FUEL LINE |
FR2765520B1 (en) | 1997-07-03 | 1999-08-27 | Nyltech Italia | MULTI-LAYER STRUCTURE BASED ON POLYAMIDES AND TUBE OR CONDUIT WITH MULTI-LAYER STRUCTURE |
EP0922731A1 (en) * | 1997-12-11 | 1999-06-16 | Wolff Walsrode Aktiengesellschaft | Blends of polyamide(s) and polyesteramide(s) |
FR2832486A1 (en) * | 2001-11-22 | 2003-05-23 | Atofina | Multilayer tubing useful for making automobile fuel pipes includes a binder layer between a layer of polyamide-polyolefin blend and an inner layer of polyamide containing an electrically conductive filler |
KR101118818B1 (en) * | 2003-02-28 | 2012-06-13 | 이엠에스-케미에 아게 | Thermoplastic multilayer composite in form of hollow body having sour-gas resistance and low temperature impact property |
JP4619624B2 (en) * | 2003-03-31 | 2011-01-26 | 旭硝子株式会社 | Laminated hose |
EP1559537B2 (en) | 2004-01-29 | 2022-12-07 | TI Automotive (Fuldabrück) GmbH | Multilayer plastic pipe with barrier properties |
DE102004036179A1 (en) | 2004-07-26 | 2006-03-23 | Degussa Ag | Coolant line |
-
2007
- 2007-07-27 CN CN2007101376290A patent/CN101125469B/en active Active
- 2007-07-27 JP JP2007195883A patent/JP5290545B2/en active Active
- 2007-07-31 US US11/831,289 patent/US8383218B2/en active Active
- 2007-07-31 KR KR1020070076843A patent/KR101014777B1/en active IP Right Grant
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5284184A (en) * | 1992-04-14 | 1994-02-08 | Itt Corporation | Corrugated multi-layer tubing having at least one fluoroplastic layer |
US6162244A (en) * | 1996-03-29 | 2000-12-19 | Willy Ruesch Ag | Layered stent |
US5960977A (en) * | 1998-05-14 | 1999-10-05 | Itt Manufacturing Enterprises, Inc. | Corrugated polymeric filler neck tubing |
US20020012806A1 (en) * | 2000-06-09 | 2002-01-31 | Ems-Chemie Ag | Thermoplastic multilayer composites |
US6555243B2 (en) * | 2000-06-09 | 2003-04-29 | Ems-Chemie Ag | Thermoplastic multilayer composites |
US20050025920A1 (en) * | 2003-02-28 | 2005-02-03 | Alex Stolarz | Thermoplastic multilayer composite in the form of a hollow body |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110178245A1 (en) * | 2010-01-15 | 2011-07-21 | Tredegar Film Products Corporation | Elastic Blends of High Density Polyethylene Polymers with Olefinic Block Copolymers |
US20110220236A1 (en) * | 2010-03-15 | 2011-09-15 | Ems-Patent Ag | Two-layered plastic tubing piece for pressurized fluid conduits |
CN102242832A (en) * | 2010-03-15 | 2011-11-16 | 埃姆斯·帕特恩特股份有限公司 | Two-layer plastic guide piece for pressurised fluid lines |
EP2402224A1 (en) * | 2010-06-30 | 2012-01-04 | Ems-Patent Ag | Brake booster pipe |
CN103282420A (en) * | 2010-12-16 | 2013-09-04 | 帝斯曼知识产权资产管理有限公司 | Polymer composition containing a polymer, which polymer contains monomer units of a dimerised fatty acid |
US20120153232A1 (en) * | 2010-12-21 | 2012-06-21 | Basf Se | Thermoplastic molding composition |
US9721695B2 (en) * | 2010-12-21 | 2017-08-01 | Basf Se | Thermoplastic molding composition |
US20120153233A1 (en) * | 2010-12-21 | 2012-06-21 | Basf Se | Thermoplastic molding composition |
JP2013086510A (en) * | 2011-10-14 | 2013-05-13 | Evonik Industries Ag | Use of multilayered sheet for manufacturing photoelectromotive force module |
CN102604373A (en) * | 2012-02-23 | 2012-07-25 | 无锡殷达尼龙有限公司 | Formula of nylon hose |
EP3144143A1 (en) * | 2015-09-16 | 2017-03-22 | Cooper-Standard Automotive, Inc. | Fuel tube for a gasoline engine |
EP3144143B1 (en) | 2015-09-16 | 2018-11-14 | Cooper-Standard Automotive, Inc. | Fuel tube for a gasoline engine |
US10914408B2 (en) | 2016-01-15 | 2021-02-09 | Arkema France | Multilayer tubular structure having better resistance to extraction in biofuel and use thereof |
US11598452B2 (en) | 2016-01-15 | 2023-03-07 | Arkema France | Multilayer tubular structure having better resistance to extraction in biofuel and use thereof |
US11339899B2 (en) | 2016-01-15 | 2022-05-24 | Arkema France | Multilayer tubular structure having better resistance to extraction in biofuel and use thereof |
US11161319B2 (en) | 2016-01-15 | 2021-11-02 | Arkema France | Multilayer tubular structure having better resistance to extraction in biofuel and use thereof |
JP2018047701A (en) * | 2016-09-21 | 2018-03-29 | エボニック デグサ ゲーエムベーハーEvonik Degussa GmbH | Multilayer hollow body having high leaching resistance |
EP3299165B1 (en) * | 2016-09-21 | 2020-08-12 | Evonik Operations GmbH | Multilayer hollow body with high washing resistance |
JP7009129B2 (en) | 2016-09-21 | 2022-01-25 | エボニック オペレーションズ ゲーエムベーハー | Multi-layer hollow body with high leaching resistance |
EP3299165A1 (en) | 2016-09-21 | 2018-03-28 | Evonik Degussa GmbH | Multilayer hollow body with high washing resistance |
US10724659B2 (en) | 2017-05-23 | 2020-07-28 | Cooper-Standard Automotive (Deutschland) Gmbh | Multilayer tube for guiding fuel fluid and method of manufacturing same |
EP3406440A1 (en) * | 2017-05-23 | 2018-11-28 | Cooper-Standard Automotive (Deutschland) GmbH | Multilayer tube for guiding fuel fluid and method of manufacturing same |
EP3689591A4 (en) * | 2017-09-29 | 2021-07-07 | UBE Industries, Ltd. | Layered tube |
US11772369B2 (en) * | 2017-12-22 | 2023-10-03 | Ems-Patent Ag | Fuel line, method for producing same, and uses thereof |
Also Published As
Publication number | Publication date |
---|---|
CN101125469A (en) | 2008-02-20 |
JP5290545B2 (en) | 2013-09-18 |
CN101125469B (en) | 2012-02-29 |
KR101014777B1 (en) | 2011-02-14 |
KR20080011632A (en) | 2008-02-05 |
US8383218B2 (en) | 2013-02-26 |
JP2008030483A (en) | 2008-02-14 |
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